Acidic cleaning compositions comprising a polymer

ABSTRACT

The present invention is directed, in certain embodiments, to compositions useful for the removal of grease, lime scale, soap scum, feces, rust or other soils from surfaces such as those found in bathrooms, toilets and kitchens. Methods of removing soils and preventing soil adhesion are also contemplated.

BACKGROUND OF THE INVENTION

Cleaning compositions for use on hard surfaces are known in the art.Hard surfaces include household surfaces such as those typically foundin bathrooms and kitchens, and include a variety of different materialssuch as enamel, ceramic, porcelain and the like. Such surfaces includefixtures such as countertops, appliances (e.g., refrigerators, stoves)as well as bathtubs, sinks, and toilets.

Acidic cleansers are known that purport to provide activity againstmineral deposits, e.g., lime scale or soap scum. Some of these cleanersare marketed as being useful for limescale and rust removal, and aresaid to be dependent upon a certain pH range to retain the desiredactivity.

However, an ongoing need exists for improved hard surface cleaners thatare effective at removing limescale, soap scum, rust, and other soildeposits from bathroom surfaces. In particular, cleaning compositionsthat are useful as toilet bowl cleaners (“TBCs”) are desirable. Becauseconsumers are often reluctant to scrub toilet surfaces, cleaningcompositions that are effective at removing solid and visible depositssuch as soil and limescale from toilet bowls while requiring little orno follow-up scrubbing or wiping are especially desirable.

SUMMARY OF THE INVENTION

A cleaning composition comprising:

-   -   (a) an organic acid;    -   (b) a nonionic surfactant comprising an ethoxylated alcohol; and    -   (c) a hydrophilic polymer that adsorbs to hard surfaces.

A composition useful for cleaning a bathroom or kitchen surface,comprising:

-   -   (a) lactic acid and phosphoric acid in a weight ratio of about        1:3 to about 3:1;    -   (b) a nonionic surfactant comprising a C₉-C₁₁ alcohol with a        degree of ethoxylation of about 7.5 to about 8.1;    -   (c) about 0.1 to about 1% of an anti-adhesion polymer comprising        a polybetaine;    -   (d) optionally a thickener chosen from xanthan gum, gellan gum,        carrageenan gum, hydroxyethylcellulose; and    -   (e) about 85 to about 95% water;        wherein the pH of the composition is 0 to about 3.

A composition useful for cleaning a bathroom or kitchen surface,comprising:

-   -   (a) oxalic acid and formic acid in a weight ratio of about 1:2        to about 1:5;    -   (b) a nonionic surfactant comprising a C₉-C₁₁ alcohol with a        degree of ethoxylation of about 7.5 to about 8.1;    -   (c) about 0.1 to about 1% of an anti-adhesion polymer comprising        a polybetaine;    -   (d) optionally a thickener chosen from xanthan gum, gellan gum,        carrageenan gum, hydroxyethylcellulose; and    -   (e) about 85 to about 95% water;        wherein the pH of the composition is 0 to about 3.

DETAILED DESCRIPTION OF THE INVENTION

As used throughout, ranges are used as a shorthand for describing eachand every value that is within the range. Any value within the range canbe selected as the terminus of the range. Furthermore, all referencescited herein are hereby incorporated by reference in their entireties.However, in the event of a conflict between a definition in the presentdisclosure and one in a cited reference, the present disclosurecontrols.

The compositions as provided herein are described and claimed withreference to their ingredients, as is usual in the art. As would beevident to one skilled in the art, the ingredients may in some instancesreact with one another, so that the true composition of the finalformulation may not correspond exactly to the ingredients listed. Thus,it should be understood that the invention extends to the product of thecombination of the listed ingredients.

In certain embodiments, the present invention is directed to acomposition that is useful for the cleaning or disinfecting of hardsurfaces such as those typically found in bathrooms and kitchens,especially enamel, glass, metal, hard plastic, tile, glass, porcelain orceramic surfaces, such as bathtubs, sinks, countertops and toilets.Other hard surfaces for which the compositions of the present inventionmay be useful include, e.g., metals such as stainless steel, and naturalor synthetic minerals such as granite.

In various embodiments, the compositions of the present invention may beuseful for the removal of soils such as, for example, grease, limescale, soap scum, feces, rust or other soils. In certain embodiments, acomposition of the present invention is an aqueous solution comprised ofan organic acid, together with a nonionic surfactant, a thickener and ananti-adhesion polymer.

In various embodiments, the invention is also directed to methods forremoving stains, e.g., those resulting from lime scale, soap scum,grease, feces or rust, from a hard surface, comprising applying thecomposition to the hard surface, and rinsing the composition, e.g., withwater, or wiping off the composition, e.g., with a sponge, towel, brushor other implement.

The compositions of the present invention comprise an organic acid. Incertain embodiments, one or more organic acids may be present. Incertain embodiments the compositions may further comprise an inorganicacid. Organic acids that are useful for the present embodiments mayinclude, for example, acetic acid, lactic acid, citric acid, levulinicacid, tartaric acid, formic acid, glycolic acid, adipic acid, succinicacid, glutaric acid, maleic acid, methane sulfonic acid, sulfamic acidand oxalic acid. Inorganic acids are optional for the present inventionand may include, for example, sulfuric acid, nitric acid, hydrochloricacid or phosphoric acid.

In various embodiments, at least one organic acid is lactic acid in anamount of about 2 to about 6% of the composition. In certainembodiments, the compositions may comprise two or more organic acids, ora combination of organic and inorganic acids, for example, formic andoxalic acids in a weight ratio of about 2:1 to about 5:1, or lactic acidand phosphoric acid in a weight ratio of about 1:3 to about 3:1.

In various embodiments, the compositions of the present invention aresuch that the total amount of acid present (including both organic andinorganic acids) is about 4 to about 7.5% of the composition, about 4.5to about 7% of the composition, or about 4.75 to about 6.75% of thecomposition.

In various embodiments, the compositions of the present invention mayfurther comprise a hydrophilic polymer that adsorbs to hard surfaces,i.e., an anti-adhesion polymer. As used herein, the term “anti-adhesionpolymer” refers to a polymer that prevents the adhesion of soils to ahard surface, either by creating a physical barrier impeding soilssticking to the surface or allowing a better flowing of the soil fromthe surface. In certain embodiments, the anti-adhesion polymer may be anamphoteric polymer, and/or may be a hydrophilic polymer.

In certain embodiments, the anti-adhesion polymer may comprise apolybetaine. For example, useful polymers that may be included in thecompositions of the present invention are those polymers available underthe tradename “Mirapol Surf S-500” or “Mirapol Surf-S 110” from Rhodia,Inc. (Tennessee, USA), and may be further described in U.S. PatentApplication Publication No. 2006/0217286 to Geoffrey et al. Other usefulpolymers include, for example, a polymeric quaternary ammonium saltconsisting of acrylamide and dimethyl dialkyl ammonium chloridemonomers, also known as Polyquaternium-7 and available, for example,under the tradename “Merquat 550” from Nalco Company (Illinois, USA); orwater-soluble polymers such as those available under the trade name“Sokalan” from BASF Company (New Jersey, USA).

In certain embodiments, the anti-adhesion polymer may be a polyacrylatepolymer. In certain embodiments, amphoteric polyamines have been foundto be useful as anti-adhesion polymers, such as those available underthe trade name “Sokalan” and available from BASF (New Jersey, USA).These include, for example, “Sokalan HP 70,” or polycarboxylates such asmaleic acid/olefin copolymers such as those available under the tradename “Sokalan CP 9” from BASF or “Acusol 460 NK (available from Rohm &Haas (Pennsylvania, USA).

The compositions of the present invention comprise a nonionicsurfactant. Examples of nonionic surfactants useful for the presentinvention include the alkoxylated alcohol nonionic surfactants, forexample, primary aliphatic alcohol ethoxylates, secondary aliphaticalcohol ethoxylates, alkylphenol ethoxylates andethylene-oxide-propylene oxide condensates on primary alkanols, such aPLURAFACS (BASF, New Jersey, USA) and condensates of ethylene oxide withsorbitan fatty acid esters such as the compositions available under thevarious TWEENS tradenames, available from ICI Surfactants (New Jersey,USA). The nonionic synthetic organic detergents generally are thecondensation products of an organic aliphatic or alkyl aromatichydrophobic compound and hydrophilic ethylene oxide groups. Practicallyany hydrophobic compound having a carboxy, hydroxy, amido, or aminogroup with a free hydrogen attached to the nitrogen can be condensedwith ethylene oxide or with the polyhydration product thereof,polyethylene glycol, to form a water-soluble nonionic detergent.Further, the length of the polyethenoxy chain can be adjusted to achievethe desired balance between the hydrophobic and hydrophilic elements.

The nonionic detergent class includes the condensation products of ahigher alcohol (e.g., an alkanol containing 8 to 18 carbon atoms in astraight or branched chain configuration) condensed with about 5 toabout 30 moles of ethylene oxide, for example, lauryl or myristylalcohol condensed with about 16 moles of ethylene oxide (EO), tridecanolcondensed with about 6 moles of EO, myristyl alcohol condensed withabout 10 moles of EO per mole of myristyl alcohol, the condensationproduct of EO with a cut of coconut fatty alcohol containing a mixtureof fatty alcohols with alkyl chains varying from 10 to 14 carbon atomsin length and wherein the condensate contains either about 6 moles of EOper mole of total alcohol or about 9 moles of EO per mole of alcohol andtallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.

In certain embodiments, the nonionic surfactants are the Neodolethoxylates (available from Shell Co., USA), which are higher aliphatic,primary alcohol containing 9 to 15 carbon atoms, such as C₉-C₁₁ alkanolcondensed with 2.5 to 10 moles of ethylene oxide (NEODOL 91-2.5 or -5 or-6 or -8), C₁₂-C₁₃ alkanol condensed with 6.5 moles ethylene oxide(Neodol 23-6.5), C₁₂-C₁₅ alkanol condensed with 12 moles ethylene oxide(Neodol 25-12), C₁₄-C₁₅ alkanol condensed with 13 moles ethylene oxide(Neodol 45-13), and the like. In certain embodiments, the nonionicsurfactant component is a mixture of Neodol 91-8 and Neodol 91-2.5 inthe range of about 7:1 to about 3:1 weight ratio.

In certain embodiments, the nonionic system comprises the mixture of anonionic surfactant formed from a C₉-C₁₁ alkanol condensed with 2 to 3.5moles of ethylene oxide (C₉-C₁₁ alcohol EO 2 to 3.5:1) with a nonionicsurfactant formed from a C₉-C₁₁ alkanol condensed with 7 to 9 moles ofethylene oxide (C₉-C₁₁ alcohol EO 7 to 9:1), wherein the weight ratio ofthe C₉-C₁₁ alcohol EO 7 to 9:1 to the C₉-C₁₁ alcohol EO 2 to 3.5:1 is,in various embodiments, about 8:1 to about 1:1, or about 7:1 to about3:1.

Additional satisfactory water soluble alcohol ethylene oxide condensatesare the condensation products of a secondary aliphatic alcoholcontaining 8 to 18 carbon atoms in a straight or branched chainconfiguration condensed with 5 to 30 moles of ethylene oxide. Examplesof commercially available nonionic detergents of the foregoing type areC₁₁-C₁₅ secondary alkanol condensed with either 9 EO (available underthe tradename “TERGITOL 15-S-9”) or 12 EO (available under the tradename“TERGITOL 15-S-12”) marketed by Union Carbide (USA).

Other suitable nonionic detergents include the polyethylene oxidecondensates of one mole of alkyl phenol containing 8 to 18 carbon atomsin a straight- or branched chain alkyl group with about 5 to about 30moles of ethylene oxide. Specific examples of alkyl phenol ethoxylatesinclude nonyl phenol condensed with about 9.5 moles of EO per mole ofnonyl phenol, dinonyl phenol condensed with about 12 moles of EO permole of phenol, dinonyl phenol condensed with about 15 moles of EO permole of phenol and di-isoctylphenol condensed with about 15 moles of EOper mole of phenol. Commercially available nonionic surfactants of thistype include those available under the tradename “IGEPAL CO-630” (nonylphenol ethoxylate) marketed by GAF Corporation (USA).

Also among the satisfactory nonionic detergents are the water-solublecondensation products of a C₈-C₂₀ alkanol with a heteric mixture ofethylene oxide and propylene oxide wherein the weight ratio of ethyleneoxide to propylene oxide is about 2.5:1 to about 4:1, preferably about2.8:1 to about 3.3:1, with the total of the ethylene oxide and propyleneoxide (including the terminal ethanol or propanol group) being 60-85%,preferably 70-80%, by weight. Such detergents are commercially availablefrom BASF-Wyandotte and a particularly preferred detergent is a C₁₀-C₁₆alkanol condensate with ethylene oxide and propylene oxide, the weightratio of ethylene oxide to propylene oxide being 3:1 and the totalalkoxy content being about 75% by weight.

Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- andtri-C₁₀-C₂₀ alkanoic acid esters having a hydrophilic-lipophilic balance(HLB) of about 8 to about 15 also may be employed as the nonionicdetergent ingredient in the described composition. These surfactants areknown and are available from Imperial Chemical Industries (New Jersey,USA) under the TWEEN trade name. Suitable surfactants includepolyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitanmonostearate, polyoxyethylene (20) sorbitan trioleate andpolyoxyethylene (20) sorbitan tristearate.

Other suitable water-soluble nonionic detergents are marketed under thetrade name PLURONICS (available from BASF, New Jersey, USA). Thecompounds are formed by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propyleneglycol. The molecular weight of the hydrophobic portion of the moleculeis of the order of 950 to 4000 and preferably 200 to 2,500. The additionof polyoxyethylene radicals to the hydrophobic portion tends to increasethe solubility of the molecule as a whole so as to make the surfactantwater-soluble. The molecular weight of the block polymers varies fromabout 1,000 to about 15,000 and the polyethylene oxide content maycomprise about 20% to about 80% by weight. Preferably, these surfactantswill be in liquid form and satisfactory surfactants are available asgrades L 62 and L 64. In certain embodiments, useful nonionics includealkyl polyglucosides.

In certain embodiments, the compositions of the present invention mayfurther comprise an organic solvent. Organic solvents that can be usedin the composition include alcohols and ethers, for example glycols oralkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols,linear alcohols, or other glycol ethers; e.g., C₁₋₄ alcohols, e.g.,ethanol or isopropanol, and glycol ethers and diethers, especially C₁₋₆alkyl ethers of propylene glycol or dipropylene glycol, for exampledipropyleneglycol monobutyl ether, propylene glycol n-butyl ether, andmixtures thereof. In certain embodiments, the solvents are present in a1:1:1 mixture of dipropylene glycol mono-butyl ether, propylene glycoln-butyl ether and ethanol. In various embodiments, this organic solventmay be present an amount by weight of about 1 to about 6%, about 2 toabout 5%, about 2.5 to about 4% or about 3% of the cleaningcompositions.

Additional optional ingredients may be included to provide added effector to make the product more attractive to consumers. Such ingredientsinclude perfumes or fragrances, colorants such as pigments or dyes,additional thickening or abrasive agents, disinfectants, radicalscavengers, hydrotropes, bleaching agents, chelating agents, or mixturesthereof.

The compositions of the present invention may be dispensed by any meansknown in the art of cleaning compositions. For example, in certainembodiments, the compositions may be dispensed by a spray bottle to thearea to be cleaned. Optionally, the pump on the spray bottle may have afoaming mechanism so that the formulation is dispensed in the form of afoam. Accordingly, in various embodiments, the invention furtherprovides a non-aerosol container containing the composition and having aspray pump so that the composition can be sprayed on the surface to becleaned, e.g., wherein the spray pump is a foam-generating pump so thatthe formulation can be dispensed in the form of a foam.

Unless otherwise stated, all percents described in the examples andelsewhere in this application are in weight percents based on the totalformulation as 100%. All tests and measurements are performed at roomtemperature and pressure unless otherwise stated. The examples and otherstatements of preferred ingredients, formulations and utilities areintended to illustrate rather than to limit the invention.

Example 1

Tables 1 and 2 illustrate some compositions of the described invention(Formulas A through H). Unless otherwise specified, all percentages areby weight.

TABLE 1 Formula A Formula B Formula C Formula D Component (Weight %)(Weight %) (Weight %) (Weight %) Phosphoric acid 2 2 3 3 Lactic acid 3 33 3 C9-C11 alcohol 2.5 2.5 3 3 EO 7.5-8:1 C9-C11 alcohol 0 0 0 0.5 EO2-3.5:1 Polymer 0.2 0.2 0.2 0.2 Solvent 0 0 3 3 Hydrotrope 0 0 0 0.4(Solubilizer) Perfume 0.4 0.4 0.4 0.4 Thickener 0.5 0.0 0.25 0 Waterq.s. q.s. q.s. q.s.

TABLE 2 Formula E Formula F Formula G Formula H Component (Weight %)(Weight %) (Weight %) (Weight %) Oxalic acid 0.5 0.5 1.0 1.0 Formic acid2.0 2.0 2.5 2.5 C9-C11 alcohol 2.5 3.0 2.5 3.0 EO 7.5-8:1 C9-C11 alcohol0 0.5 0 0.5 EO 2-3.5:1 Polymer 0.2 0.2 0.2 0.2 Hydrotrope 0 0.4 0 0.4(Solubilizer) Solvent 0 3 0 3 Perfume 0.4 0.4 0.4 0.4 Thickener 0.25 00.5 0 Water q.s. q.s. q.s. q.s.

The compounds of Formulas A to H demonstrated excellent performance inlime scale, artificial feces and soap scum prevention, have a clearactivity against rust, while still retaining substantial effectivenessagainst grease.

What is claimed is:
 1. A cleaning composition comprising: (a) formic andoxalic acids in a weight ratio of about 2:1 to about 5:1; (b) a nonionicsurfactant comprising an ethoxylated alcohol; and (c) a polybetaine. 2.The cleaning composition of claim 1, wherein: the nonionic surfactantcomprises a C₉-C₁₁ alcohol with a degree of ethoxylation of about 7 toabout
 9. 3. The composition of claim 1, wherein the nonionic surfactantis a C₉-C₁₁ alcohol with a degree of ethoxylation of about 7.5 to about8.1.
 4. The composition of claim 1, further comprising an inorganic acidchosen from phosphoric acid, nitric acid, hydrochloric acid and sulfuricacid.
 5. The composition of claim 1, wherein the total amount of acidpresent is between about 4 and about 7.5% of the composition.
 6. Thecomposition of claim 5, wherein the total amount of acid present isbetween about 4.5 and about 7% of the composition.
 7. The composition ofclaim 1, further comprising a thickener comprising xanthan gum, gellangum, carrageenan gum, hydroxyethylcellulose and mixtures thereof.
 8. Acomposition useful for cleaning a bathroom or kitchen surface,comprising: (a) formic and oxalic acids in a weight ratio of about 2:1to about 5:1; (b) a nonionic surfactant comprising a C₉-C₁₁ alcohol witha degree of ethoxylation of about 7.5 to about 8.1; (c) about 0.1 toabout 1% of an anti-adhesion polymer comprising a polybetaine; (d)optionally a thickener comprising xanthan gum, gellan gum, carrageenangum, hydroxyethylcellulose; and (e) about 85 to about 95% water; whereinthe pH of the composition is 0 to about
 3. 9. A cleaning systemcomprising the composition of claim 1 contained within a jug or spraybottle.
 10. A method of removing soil or limescale from a hard surfacecomprising applying the composition of claim 1 to the hard surface andrinsing or wiping the hard surface.
 11. The method of claim 10, whereinthe hard surface is the surface of a toilet.
 12. A method ofdisinfecting a hard surface comprising applying the composition of claim1 to the surface and rinsing or wiping the surface.
 13. A method ofpreventing soil adhesion to a hard surface comprising applying thecomposition of claim 1 to the surface and rinsing or wiping the surface.14. A method of imparting shine to a hard surface comprising applyingthe composition of claim 1 to the hard surface.
 15. A cleaning systemcomprising a non-aerosol container containing the composition of claim 1and comprising a spray pump for dispensing the composition.
 16. Thecleaning system of claim 15, wherein the spray pump is a foam-generatingpump, allowing the composition to be dispensed in the form of a foam.17. A method of removing a soil from a surface comprising the step ofapplying the composition of claim 1 onto the hard surface, and rinsingor wiping the surface.
 18. The method of claim 17, wherein the soil ischosen from grease, limescale, soap scum or feces.
 19. A method ofpreventing the adhesion of a soil to a hard surface, comprising the stepof applying the composition of claim 1 onto the hard surface, andrinsing or wiping the hard surface.